Certain oximinophosphonodithioates and their use as insecticides and acaricides

ABSTRACT

Compounds having the formula   IN WHICH R is (1) alkyl or (2) allyl; R1 is alkyl; R2 is alkyl; and R3 is (1) hydrogen, (2) lower alkylthio, (3) cyano, (4) phenylthio, (5) substituted phenylthio wherein the substituent is halogen, (6) ethynyl, or (7) CC12 CH-, are used as insecticides and acaricides.

United States Patent 1 Gutman m 3,760,072 145-1 Sept. 18, 1973 [5 1 CERTAIN v oxmmornosrnouomrmonns AND THEIR use AS INSECTICIDES AND ACARlClDES [75] Inventor: Arnold D. Gutman, Berkeley, Calif.

[73] Assignee: Staulfer Chemical Company, New

York, N.Y.

22 Filed: Nov. 22, 1971 21 App1.No.:201,170

Related US. Application Data [62] Division of Ser. No. 26,149, April 6, 1970, Pat. No.

2,957,016 10/1960 Diamond ..260/944X 3,652,736 3/1972 Primary ExaminerA1bert T. Meyers Assistant Examiner-Vincent D. Turner Attorney-Daniel C. Block et a1.

[57] ABSTRACT Compounds having the formula in which R is (1) alkyl or (2) allyl; R is alkyl; R is alkyl; and R is 1) hydrogen, (2) lower alkylthio, (3) cyano, (4) phenylthio, (S) substituted phenylthio wherein the substituent is halogen, (6) ethynyl, or (7) CC1 =Cl-l, are used as insecticides and acaricides.

10 Claims, N0 Drawings Gutman 424/211 CERTAIN oxmmornosruouomrmonrss AND THEIR use AS mssc'ncmas AND ACARICIDES formula s BCl-In-R' R15 EU in which R is l alkyl having 1 to 4 carbon atoms, preferably branched chained, more preferably methyl and t-butyl or (2) ally]; R is alkyl having 1 to 4 carbon atoms preferably methyl; R is alltyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms and R is 1) hydrogen; (2) lo'wer'alk'ylthio having 1 to 4 carbon atoms; (3) cyano; (4) phenylthio; (5) substituted phenylthio wherein the substituent is halogen preferably, chlorine; (6) ethynyl, or (7) CCI,=CH.

The compounds of the present invention can be prepared according to the following reactions:

Cl SCHIR' NaOH 4- 1150mm in which R, R, R, and. R are as defined.

In the event that the desired compound cannot be prepared because of difficulty of preparing or obtaining the compound HSCl-hR of reaction l(B), then the following reaction can be utilized to obtain the compounds of this invention. I

recited in reaction l(A) and KB) were R and R are as defined can e epa e according t9 e e e a P cedure stated in Belgium Pat. No. '7 l0,64 9"by reaction of the appropriate xyanthate, with hydroxyl amine hydrochloride followed by reaction with the appropriate alkyl halide.

Preferably, reaction [(A) is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used, the reaction still proceeds but yields are reduced. The reactants can be combined in any desired manner but preferably, the reaction is run in a solvent such as THF by first preparing the salt of the oxime reactant with an acid acceptor such as potassium t-butoxide at room temperature and then preferably, slowly adding the dichloride reactant thereto, preferably in solution with a solvent, for example, THF, at a temperature below about 15C. for control. However, the oxime reactant can be used in place of the salt, preferably in the presence of the acid acceptor. The resulting produce is recovered and purified by standard procedure. For example, the resulting product can be recovered from the reaction mixture and purified from the reaction mixture by adding the mixture to a non-P lar solvent such as benzene. The benzene mixture is then washed with water, dilute NaOH solution and then again by water. The benzene is evaporated after the water has been removed, for example, by treatment with anhydrous MgSO, to yield the purified P oduc Reaction K3) is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used, the reaction still proceeds but yields are reduced. The reaetants ean be combined in any manner but preferably the phosphorus-containing reactant is slowly added to the reactant containing the SH group in a solvent such as THF, preferably with stirring. More preferably, an alkalimetal salt of this reactant is used to reduce the change of a violent reaction. The temperature of the reaction is not critical, however, better-yields are obtained by heating the reactants at reflux for a time sufficient to allow completion of the reaction. The resulting product can be recovered from the reaction mixture and purified by standard procedures. For example, the desired reaction product can be recovered from the reaction mixture by adding'the mixture to a non-polar solvent such as benzene. The benzene mixture is then washed with water, dilute NaOl-l solution and then again by water. The benzene is evaporated after the water has been removed, for example, by treatment with anhydrous MgSO, to yield the purified product.

I The process of this invention is represented by reaction II(A) and gives intermediate compounds useful to prepare the compounds of this invention. In other words, the process of this invention is a process for preparing acompound having the formula:

RO SE in which R, R, and R are as defined comprising reacting a compound of the formula in which R and R are as defined with a compound of the formula in which R is as defined.

The process of this invention is carried out by merely reacting the two reactants. Preferably, about 2 moles of the oxime reactant per mole thionophosphine sulfide reactant should be used. If other proportions of either reactant are used, the reaction still proceeds but yields are lowered. The reactants can be combined in any desired manner. The reaction readily proceeds at room temperature and preferably is run under anhydrous conditions in a solvent such as benzene. The dithiophosphonic acid product can be recovered from its solvent in pure form, but it is preferred to not do so. If prolonged storage of the compound is desired, it is preferable to prepare either the alkali, alkaline, or heavy metal salt of the acid.

Another process of this invention is represented by reaction ll(B) which utilizes as a reactant the product of reaction ll(A) preferably as a solution in the solvent utilized for reaction ll(A).

In this process, the reaction is carried out by reacting preferably about equal mole amounts of the reactants. If an excess of either reactant is used, the reaction still proceeds but again yields are lowered. Although the reactants can be combined in any desired manner, it is preferred to add the halide reactant to a solution of the dithiophosphonic acid reactant, preferably the acid is not recovered from the solvent in which it is prepared. Preferably, the reaction is carried out at below room temperature about 20C. for control and in the presence of a base, such as triethyl amine, to take up the liberated acid halide reaction product. The reaction product is recovered by conventional means such as described for reaction [(8).

The novel intermediate compounds of this invention which are l useful in preparing the compounds of this invention, for example, by reaction (13), heretofore described or (2) as insecticides or acaricides, are those having the formula:

in which R is (1) alkyl having 1 to 8 carbon atoms, methyl or (2) lower alkylthiomethyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; R is alkyl having 1 to 4 carbon atoms, preferably methyl and R is alkyl having 1 to 4 carbon atoms, preferably 1 to.2 carbon atoms.

These intermediate compounds are preferable according to reaction II(A) and the subsequent discussion thereof.

If desired, the alkali, alkaline earth or heavy metal salts of the intermediate acid compounds can be prepared by convention techniques such asby reacting the acid with a base. The salts will either be mono, di or tri basic depending upon the valency of the metal atom used to form the salt.

Preparation of the compounds of this invention, the process for preparing intermediates and the intermediates are illustrated by the following examples:

EXAMPLE I C2Ha0 8/8 H =Nol CHI 5 CgHs O-(O-ethyl-S-methylthioformaldoximino), ethyl-dithiophosphonic acid This example teaches the synthesis of the oximino, ethyl phosphonic acid useful in the preparation of the compounds of this invention.

12.4 grams (0.05 moles) of ethylthionophosphine sulfide is combined with 200 ml. of anhydrous benzene in a 1000 ml. beaker. The mixture is magnetically stirred at room temperature, and 13.5 grams (0.1 mole) of O- ethylmethylthioformaldoxime is added, and the resulting mixture is stirred for 30 minutes until a clear solution is obtained. The benzene is evaporated to yield the desired product. LR. confirms the desired product.

EXAMPLE ll CHa O-(O-ethyl,S-methylthioformaldoximino), propargyl phosphonodithioate 12.4 grams (0.05 mole) of ethylthiophosphine sulfide is combined with 200 ml. of anhydrous dioxane in a 1000 ml. beaker, and 13.5 gms. (0.1 mole) of O-ethyl, methylthioformaldoxime is added. The mixture is stirred magnetically at room temperature until a clear solution containing the compound of Example I is obtained. The solution is cooled in an ice bath to 10C., and l 1.9 gms. (0.1 mole) of propargylbormide is added followed by 15.1 gms. (0.15 mole) of triethylamine added over a period of 10 minutes. The resulting mixture is stirred at room temperature for one hour, then poured into 300 ml. of benzene. The benzene mixture is washed with 200 ml. of H 0, ml. of saturated NaHCO followed by 2 100 ml. portions of H 0. The benzene phase is dried with anhydrous MgSO, and evaporated under reduced pressure to yield 27 gms. (90.3 percent of theory) of the desired compound. N =1 .5643. v

The following is a table of certain selected compounds that are preferable according to the procedure described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

ethyl-S- TABLE I R 8 CII R H 'NO l [U S R Compound number R R R N 1 CzHs CH C 115 CECH 1.5693 CzHa CH C2H5 CEN 1.5618 CgH5 CH3 C111,, CI1=CC]2 1.5705 CgHs CH3 02H; -SCH2CH 1,5545

CzHs CH3 C2115 l. 5925 01H; CH CgHs H l. 5541 CH2=CHCH: CH3 C2115 CEN 1. 5838 CHg==CHCHg CH: Cal-I CECH 1. 5327 CHz=CHCHz- CH C211 --S CH 1,5990 CHz=CHCHz CH3 CzHs SCHzCHa 1.5937

'1 Prepared in Example II. The following tests illustrate utility of the compounds as insecticides and acaricides.

INSECTICIDAL EVALUATION TESTS quots of this solution were combined with l milliliter of an acetone-peanut oil solution in an aluminum dish and allowed to dry. The aliquots were there to achieve desired toxicant concentration ranging from 100 pg. per dish to that at which 50 percent mortality was attained. The dishes were placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female houseflies, 3 to 5 days old, were introduced into the cage and the percent mortality was recorded after 48 hours. The LD-50 values are expressed in terms of ug. per 25 femal flies. The results of these insecticidal evaluation tests are given in Table II under HF.

In the German Cockroach (GR) tests, 10 l-month old nymphs were placed in separate circular cardboard cages sealed on one end with cellophane and covered by a cloth netting on the other. Aliquots of the toxicants, dissolved in an appropriate solvent, were dilute in water containing 0.002 percent of a wetting agent, Sponto 22l-(a polyoxyether of alkylated phenols blended with organic sulfonates). Test concentrations ranged from 0.1 percent downward to that at which 50 percent mortality was obtained. Each of the aqueous suspensions of the candidate compounds was sprayed onto the insects through the cloth netting by means of a hand-spray gun. Percent mortality in each case was recorded after 72 hours, and'the LD-SO values, expressed as a percent of toxicant in the aqueous spray, were recorded. These values are reported under the column GR in Table II.

For testing the Salt-Marsh Caterpillar, test solutions were prepared in an identical manner and at concentrations the same as for the German Cockroach above. Sections of bitter dock, Rumex obtusifolus, leaves, l-l.5 inches in length were immersed in the test solutions for 10 to 15 seconds and placed on a wire screen to dry. The dried leaf was placed on a moistened piece of filter paper in a Petri dish and infested with 5 3rd lnstar larvae. Mortality of the larvae was recorded after 72 hours and the LD-SO values are expressed as percent active ingredient in the aqueous suspension.

The Lygus Bug (LB), Lygus hesperus, was tested similarly as the German Cockroach. The cages insects were sprayed with the candidate compounds at concentrations ranging from 0.05 percent downward to that at which 50 percent mortality was obtained. After 24 and 72 hours, counts were made to determine living and dead insects. The LD-SO (Percent) values were calculated. These values are reported under the Column LB in Table II.

The insect species black bean aphid (BA), Aphis fabae (Scop), was also employed in the test for insecticidal activity. Young nasturtium, (Tropaeolum sp.), plants, approximately 2 to 3 inches tall, were used as the hose plants for the bean aphid. The host plant was infested with approximately 50 75 of the aphids. The test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221, an emulsifying agent. The solution was applied as a spray to the infested plants. Concentrations ranged from 0.05 percent downward until an LD value was achieved. These results are given in Table II under the Column ACARICIDAL EVAULATION TEST The two-spotted mite (28M), 'Tetranychus urticae (Koch), was employed in tests for miticides. Young pinto bean plants or lima bean plants (Phaseolus sp.) in the primary leaf stage were used as the host plants. The young pinto bean plants were infested with about mites of various ages. Dispersions of candidate materials were prepared by dissolving 0.1 gram in 10 ml. of a suitable solvent, usually acetone. Aliquots of the toxicant solutions were suspended in water containing 0.002 percent v/v Sponto, polyoxyethylene ether sorbitan monolaurate, an emulsifying agent, the amount of water being sufficient to give concentrations of active ingredient ranging from 0.05 percent to that at which 50 percent mortality was obtained. The test suspensions were then sprayed on the infested plants to the point of run off. After seven days, mortalities of postembryonic and ovicidal forms were determined. The percentage of kill was determined by comparison with control plants which had not been sprayed with the candidate compounds. The LD-SO values were calculated using well-known procedures. These values are reported under the columns ZSM-PE and 25M- Eggs" in Table ll.

SYSTEMIC EVAULATION TEST This text evaluates the root absorption and upward translocation of the candidate systemic compound. The two-spotted mite (28M), Tetranychus urlicae (Koch), and the Bean Aphid (BA), Aphis fabae (Scop.), were employed in the test for systemic activity.

Young pinto bean plants in the primary leaf stage were used as host plants for the two-spotted mite. The pinto bean plants were placed in bottles containing 200 ml. of the test solution and held in place with cotton plugs. Only the roots were immersed. The test solutions were prepared by dissolving the compounds to be tested in a suitable solvent, usually acetone, and then diluting with distilled water. The final acetone concentration never exceeded about 1 percent. The toxicants were initially tested at a concentration of IO parts per million (p.p.m.). Immediately after the host plant was placed in the test solution, it was infested with the test species. Mortalities were determined after seven days.

Young nasturtium plants were used as the host plants for the Bean Aphid. The host plants were transplanted TABLE II such as sodium lauryl sulfate, sodium naphthalene sulfonate, sodium alkyl naphthalane, sulfonate. melhyl cellulose, fatty alcohol ethers, polyglycol fatty acid as ters and other polyoxyethylene surface active agents. The proportion of these agents commonly comprises 1 15 percent by weight of the pesticidal compositions although the proportion is not critical and may be varied to suit any particular situation.

I claim:

1. A method of controlling acarids comprising applying thereto an acaricidally effective amount of a compound having the formula s SCHr-R o N-oin which R is (1) alkyl having 1 to 4 carbon atoms, M or (2) allyl; R is alkyl having 1 to 4 carbon atoms; R is alkyl having from l to 4 carbon atoms, and R is (1) hydrogen; (2) lower alkylthio having 1 to 4 carbon atoms; (3) cyano; (4) phenylthio; (5 substituted phenylthio wherein the substituent is halogen; (6) ethynyl; or (7) CCl =CH-.

2. The process of claim 1 in which R is ethyl, R is methyl, R is ethyl, and R is cyano.

3. The process of claim 1 in which R is ethyl, R is methyl, R is ethyl and R is ethylthio.

4. The process of claim 1 in which R is ethyl, R is methyl, R is ethyl and R is hydrogen.

5. The process of claim 1 in which R is allyl, R is methyl, R is ethyl and R is cyano.

6. A method of controlling insects comprising apply- LDso values Compound HF, GR, LB, SMC, BA, BA-SYS, PE, Eggs, SYS, number Ug. percent percent percent percent p.p.m. percent percent p.p.in.

As those in the art are well aware, various techniques are available for incorporating the active component or toxicant in suitable pesticidal compositions, thus, the pesticidal compositions can be conveniently prepared in the form of liquids or solids, the latter preferably as homogeneous free-flowing dust commonly formulated by admixing the active component with finely divided solids or carriers as exemplified by talc, natural clays, diatomaceous earth, various flours such as walnut shell, wheat, soya bean, cottonseed and so forth.

Liquid compositions are also useful and normally comprise a dispersion of the toxicant in a liquid media, although it may be convenient to dissolve the toxicant directly in a solvent such as kerosene, fuel oil, xylene alkylatecl naphthalenes or the like and use such organic solutions directly. However, the more common procedure is to employ dispersions of the toxicant in an aqueous media and such compositions may be produced by forming a concentrated solution of the toxicant in a suitable organic solvent followed by dispersion in water, usually with the aid of surface active agents. The latter, which may be the anionic, cationic, or nonionic types, are exemplified by sodium stearate, potassium oleate and other alkaline metal soaps and detergents ing thereto an insecticidally effective amount of a compound having the formula SCHn-R in which R is (1) alkyl having 1 to 4 carbon atoms, or (2) allyl; R is alkyl having 1 to 4 carbon atoms; R is alkyl having 1 to 4 carbon atoms, and R is (l) hydrogen; (2) lower alkylthio having 1 to 4 carbon atoms; (3) cyano; (4) phenylthio; (S) substituted phenylthio wherein the substituent is halogen, (6) ethynyl, or (7) CCl CH-.

7. The process of claim 6 in which R is ethyl, R is methyl, R is ethyl, and R is cyano.

8. The process of claim 6 in which R is ethyl, R is methyl, R is ethyl, and R is ethylthio.

9. The process of claim 6 in which R is ethyl, R is methyl, R is ethyl and R is hydrogen.

10. The process of claim 6 in which R is allyl, R is methyl, R is ethyl and R is cyano. 

2. The process of claim 1 in which R is ethyl, R1 is methyl, R2 is ethyl, and R3 is cyano.
 3. The process of claim 1 in which R is ethyl, R1 is methyl, R2 is ethyl and R3 is ethylthio.
 4. The process of claim 1 in which R is ethyl, R1 is methyl, R2 is ethyl and R3 is hydrogen.
 5. The process of claim 1 in which R is allyl, R1 is methyl, R2 is ethyl and R3 is cyano.
 6. A method of controlling insects comprising applying thereto an insecticidally effective amount of a compound having the formula
 7. The process of claim 6 in which R is ethyl, R1 is methyl, R2 is ethyl, and R3 is cyano.
 8. The process of claim 6 in which R is ethyl, R1 is methyl, R2 is ethyl, and R3 is ethylthio.
 9. The process of claim 6 in which R is ethyl, R1 is methyl, R2 is ethyl and R3 is hydrogen.
 10. The process of claim 6 in which R is allyl, R1 is methyl, R2 is ethyl and R3 is cyano. 